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WO1987005599A1 - Alcools tertiaires - Google Patents

Alcools tertiaires Download PDF

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Publication number
WO1987005599A1
WO1987005599A1 PCT/EP1987/000132 EP8700132W WO8705599A1 WO 1987005599 A1 WO1987005599 A1 WO 1987005599A1 EP 8700132 W EP8700132 W EP 8700132W WO 8705599 A1 WO8705599 A1 WO 8705599A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydroxy
cyclohexane
carboxylic acid
ester
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1987/000132
Other languages
German (de)
English (en)
Inventor
Andreas WÄCHTLER
Rudolf Eidenschink
Joachim Krause
Hans-Adolf Kurmeier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19863608502 external-priority patent/DE3608502A1/de
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Priority to DE8787901477T priority Critical patent/DE3768393D1/de
Publication of WO1987005599A1 publication Critical patent/WO1987005599A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings

Definitions

  • the invention relates to tertiary alcohols of the formula I.
  • a 1 1,4-phenylene or 1,4-cyclohexylene which is unsubstituted or mono- or polysubstituted by halogen and / or C H3 groups,
  • a 2 1,4-phenylene which is unsubstituted or substituted one or more times by halogen and / or CH 3 groups, an alicyclic fragment,
  • Q 2 and Q 3 do not both mean a single bond, as well as their metal alcoholates and a process for the preparation of these compounds.
  • Tertiary alcohols of the formula I are of great interest as intermediates for the preparation of liquid-crystalline compounds.
  • the object of the present invention was to find correspondingly easily synthesizable intermediates for the production of liquid crystals and a process for their production.
  • the object was achieved by providing the tertiary alcohols of the formula I and a process for their preparation.
  • p-Substituted phenylcyclohexane carboxylic acids and their esters are e.g. B. prepared by reacting cyclohexene with acetyl chloride / AlCl 3 and with benzene and then haloform degradation of the ketone to carboxylic acid, (described in J. Amer. Chem. Soc. 67, 1045 (1945), WS Johnson et al. And by Nenitzescu et al., Ann. 519 (260) 1935).
  • the substituent in the p-position, e.g. B. OCH 3 must then be introduced via electrophilic aromatic substitution (eg nitration, reduction, diazotization, introduction of the OH group and methylation), which is a very expensive route.
  • Another example describes the process for the preparation of 4- [4- (trans-4-alkylcyclohexyl) phenyl] cyclohexanecarboxylic acids (according to EP 90 671) by reduction of 4- [trans-4-alkylcyclohexyl] biphenyl-4-carboxylic acid with metallic sodium in isoamyl alcohol.
  • the disadvantages of this process are a very high consumption of reducing agent and relatively low yields.
  • a process for the preparation of compounds of the formula I is also known, in which corresponding Grignard compounds are reacted with cyclohexanones, described in J. Org. Chem. 39, 2787.
  • the object of the present invention was therefore also to find a production process for the compounds of the formula I which did not have the described disadvantages of the previous processes or only did so to a small extent.
  • zirconium or organotitanium compounds are outstandingly suitable for the preparation of compounds of the formula I.
  • the invention thus relates to the compounds of the formula I ',
  • R 1 , A 1 , Z 1 , m, A 2 , Y, Q 3 and Z 2 have the meanings given and
  • the invention furthermore relates to the use of the compounds of the formula I as intermediates for the production of liquid crystals.
  • Phe in the following means an unsubstituted or 1,4-phenylene group which is mono- or polysubstituted by halogen and / or CH 3 groups
  • Cy is an unsubstituted or mono- or polysubstituted by halogen and / or CH 3 groups 1 4-cyclohexylene group and X the group
  • the compounds of sub-formula Ib preferably include those of sub-formulas Iba and Ibb:
  • the compounds of sub-formula Ic preferably include those of sub-formulas Ica to Icf:
  • the compounds of sub-formula Id preferably include those of sub-formulas Ida to Idd:
  • the compounds of sub-formula le preferably include those of sub-formulas Iea to Ied:
  • the compounds of the sub-formula Ig preferably include those of the sub-formula Iga to Igd:
  • R 1 preferably denotes an alkyl group with 1-15 C atoms, in which one or two are not adjacent
  • a 2 preferably denotes unsubstituted 1,4-phenylene, furthermore also 1,4-phenylene monosubstituted by halogen.
  • F, Cl or Br, in particular F, are preferred as halogen.
  • n preferably denotes 1 or 2, in particular 1.
  • Z 1 has primarily the meaning of a single bond, secondly Z 1 means -CH 2 CH 2 -, further also -OCH 2 - or -CH 2 O-.
  • a 1 is preferably unsubstituted 1,4-phenylene or 1,4-cyclohexylene. If these groups are substituted, monosubstitution by F, Cl or Br, in particular monofluorosubstitution, is preferred.
  • the alicyclic fragment can be made from
  • Q 3 in the formulas above and below means alkylene with 1 to 15 C atoms, preferably with 1-10 C atoms, in particular with 1-5 C atoms, and accordingly preferably means methylene, ethylene, propylene, butylene, pentylene , Hexylene, heptylene, oetylene, nonylene or deeylene, or also alkylidene with 2-15 C atoms, preferably 2-7 C atoms, and accordingly preferably means ethylidene, propylidene, butylidene, pentylidene, hexylidene or heptylidene, furthermore also octylidene, Nonylidene or decylidene. Furthermore, Q 3 also means an aromatic system or
  • Z 2 represents -COOR or -CN, preferably an ester group.
  • R denotes alkyl with 1-15 C atoms, preferably with 3-15 C atoms, particularly preferably with 5-15 C atoms.
  • Y means H, CN or R, preferably H.
  • R has the meaning given above.
  • R or R 1 preferably denotes straight-chain or branched alkyl
  • 1-15 C atoms preferably with 2-10 C atoms, therefore preferably denotes ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, and also also methyl, undecyl, docdecyl, tridecyl, tetradecyl or pentadecyl .
  • Branched radicals such as isopropyl, 2-butyl, isopentyl, 1-methylpentyl, 2-methylpentyl, 1-methylhexyl or 1-methylheptyl are also preferred.
  • R 1 preferably also means ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy or decoxy, also also methoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy or pentadecoxy or isopropoxy, isopentoxy, 2-butoxy or 1-methylpentoxy.
  • R in Y and COOR can be the same or different.
  • the process according to the invention is based on the easily accessible aryl halides. These are transferred to Grignard reagents or lithiated using known methods, then the reaction takes place with a chlorotrialkyl orthotitanate or zirconate to give the corresponding aryltitanium trialkoxide or arylzirconium trialkoxide.
  • This reaction is preferably carried out in an inert solvent, such as. B. tetrahydrofuran, diethyl ether, benzene, toluene, hexane, etc. or in suitable mixtures of these solvents and at temperatures from -78 ° C to 100 ° C, preferably at -15 ° C to 50 ° C.
  • the corresponding keto compound is added, likewise in an inert solvent mentioned above and at the temperatures indicated.
  • the organometallic compound selectively adds to the keto group (cf. Angew. Chem. 95, 12 (1983)) to form the corresponding metal alcoholate, which contains, for example, magnesium, lithium, titanium or zirconium as metal.
  • This alcoholate is then converted in the usual way into the corresponding tertiary alcohol, which can be easily dehydrated.
  • the compounds of the formula I obtained in this way can be used for the synthesis of liquid crystal compounds and can easily be further processed into a wide variety of end products.
  • the compounds of formula IV are also new and are therefore also an object of the invention.
  • the starting compounds are keto compounds of the formula II and aryl halides of the formula VI
  • R 1 , A 1 , Z 1 , m and A 2 have the meaning given in formula I and halogen is fluorine, chlorine, iodine or bromine.
  • halogen is fluorine, chlorine, iodine or bromine.
  • the corresponding bromides are preferably also the chlorides or iodides.
  • keto compounds All cyclic keto esters or ketonitriles of the formula II which can be used are suitable as keto compounds:
  • Y, Q 3 and Z 2 have the specified, preferred
  • the trialkoxy-chlorine compounds in particular the chlorotitanium or chlorozirconium triisopropoxide, are preferably used as the zirconium or organic titanium reagent.
  • the organotitanium compounds are preferred.
  • the process according to the invention can thus be applied to any cyclic keto esters, with the exception of ⁇ -keto esters, ketonitriles and the corresponding aryl halides, which can be converted into an organometallic compound.
  • keto compounds of the formula II used as starting compounds are, for. T. known, e.g. B. the compounds VIIa or VIIb, which are described in DE-OS 34 07 113:
  • Formula II also includes new compounds of. Formula II '
  • R 2 is alkyl with 2-15 C atoms
  • Y has the meaning given above
  • R 3 is CN or COOR 4 , which are also the subject of the invention.
  • R 4 means alkyl with 3-15, preferably with 5-15, carbon atoms.
  • Mp melting point. Percentages above and below mean percentages by weight; the temperatures are given in degrees Celsius.
  • a solution of 0.1 M TiCl [OCH (CH 3 ) 2 is added to a Grignard reagent, prepared from 0.1 m 4-bromoanisole in 100 ml THF and 0.11 m magnesium shavings in 20 ml THF, at 40 ° ] 3 in 50 ml of THF and stirred for 30 minutes. Then 0.1 M cyclohexanone-4-carboxylic acid ethyl ester in 50 ml THF is added at 30-40 ° and the reaction mixture is stirred for several hours. The resulting tertiary alcohol can either be isolated in the usual way or dehydrated immediately afterwards without isolation.
  • Pentyl 1-hydroxy-1- (4-hexyloxybiphenyl-4'-yl) -cyclohexane-4-carboxylate

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des alcools tertiaires de formule (I), où R1, A1, Z1, m, A2, Q1, Q2, Q3 et Z2 ont les significations de la revendication 1, et procédé pour la production desdits alcools.
PCT/EP1987/000132 1986-03-14 1987-03-07 Alcools tertiaires Ceased WO1987005599A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE8787901477T DE3768393D1 (de) 1986-03-14 1987-03-07 Alicyclische verbindungen.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19863608502 DE3608502A1 (de) 1986-03-14 1986-03-14 Verfahren zur herstellung von tertiaeren alkoholen mit titanorganischen verbindungen
DEP3608502.2 1986-03-14
DE19873703145 DE3703145A1 (de) 1986-03-14 1987-02-03 Verfahren zur herstellung von tertiaeren alkoholen mit metallorganischen verbindungen
DEP3703145.7 1987-02-03

Publications (1)

Publication Number Publication Date
WO1987005599A1 true WO1987005599A1 (fr) 1987-09-24

Family

ID=25841959

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1987/000132 Ceased WO1987005599A1 (fr) 1986-03-14 1987-03-07 Alcools tertiaires

Country Status (5)

Country Link
US (1) US5068389A (fr)
EP (1) EP0261160B1 (fr)
JP (1) JPS63502831A (fr)
DE (2) DE3703145A1 (fr)
WO (1) WO1987005599A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4016130C2 (de) * 1990-05-18 2000-06-21 Merck Patent Gmbh Phenylcyclohexane und flüssigkristallines Medium

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5759443A (en) * 1996-07-26 1998-06-02 Rolic Ag Cyclopentyl derivatives
TWI239997B (en) * 1998-02-04 2005-09-21 Merck Patent Gmbh Liquid-crystal composition, method of adjusting the resistance of a liquid-crystal composition, liquid-crystal display and substituted phenols

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1325056A (en) * 1969-08-22 1973-08-01 Bristol Myers Co Phenyl-cyclohexane carboxylic acids and derivatives thereof
US3838172A (en) * 1967-08-22 1974-09-24 Ortho Pharma Corp Aryl substituted-hydroxy substituted cyclohexanecarboxylic acids

Family Cites Families (25)

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DE2636684C3 (de) * 1976-08-14 1980-06-19 Merck Patent Gmbh, 6100 Darmstadt Phenylcyclohexanderivate und ihre Verwendung in flüssigkristallinen Dielektrika
DE2701591C3 (de) * 1977-01-15 1979-12-20 Merck Patent Gmbh, 6100 Darmstadt Hexahydroterphenylderivate und deren Verwendung in flüssigkristallinen Dielektrika
CA1106406A (fr) * 1977-11-21 1981-08-04 Takashi Inukai Cristaux liquides
AT364000B (de) * 1978-01-30 1981-09-10 Bbc Brown Boveri & Cie Fluessigkristallsubstanz
DE2927277A1 (de) * 1979-07-06 1981-01-08 Merck Patent Gmbh Cyclohexylbiphenyle, verfahren zu ihrer herstellung, diese enthaltende dielektrika und elektrooptisches anzeigeelement
DE2948836A1 (de) * 1979-12-05 1981-06-11 Merck Patent Gmbh, 6100 Darmstadt Partiell hydrierte oligo-1,4-phenylene, diese enthaltende dielektrika und elektrooptisches anzeigeelement
DE3006666A1 (de) * 1980-02-22 1981-09-17 Merck Patent Gmbh, 6100 Darmstadt Phenylcyclohexenderivate, verfahren zu ihrer herstellung, diese enthaltende fluessigkristalline dielektrika und elektrooptisches anzeieelement
CH644574A5 (de) * 1980-06-02 1984-08-15 Merck Patent Gmbh Anisotrope cyclohexenverbindungen und fluessigkristallmischungen.
JPS574927A (en) * 1980-06-12 1982-01-11 Chisso Corp 4'-substituted-1'-cyclohexen-1'-yl-4-fluorobenzene
JPS5711935A (en) * 1980-06-25 1982-01-21 Chisso Corp 4'-alkyl-1'-cyclohexene-1'-yl-4-methoxybenzene
US4405488A (en) * 1980-10-09 1983-09-20 Chisso Corporation Liquid-crystalline halogenobenzene derivatives
DE3100142A1 (de) * 1981-01-07 1982-08-12 Merck Patent Gmbh, 6100 Darmstadt Cyclohexylcarbonitrilderivate, diese enthaltende dielektrika und elektrooptisches anzeigeelement
JPS57158729A (en) * 1981-03-26 1982-09-30 Chisso Corp 4-substituted-(4'-(4"-alkylphenyl)cyclohexen-1'-yl)benzene
US4406814A (en) * 1981-04-10 1983-09-27 Eaton Corporation Liquid crystalline materials and optical displays utilizing same
DE3223637C2 (de) * 1981-07-09 1983-09-01 Chisso Corp., Osaka Cyano-mono- oder -diphenylbicyclohexanderivate sowie deren Verwendung in Flüssigkristallzusammensetzungen
DE3211601A1 (de) * 1982-03-30 1983-10-06 Merck Patent Gmbh Hydroterphenyle
US4502974A (en) * 1982-03-31 1985-03-05 Chisso Corporation High temperature liquid-crystalline ester compounds
DE3382646D1 (de) * 1982-08-26 1993-01-28 Merck Patent Gmbh Cyclohexanderivate und ihre verwendung als komponenten fluessigkristalliner-dielektrika.
GB8319849D0 (en) * 1983-07-22 1983-08-24 Secr Defence Compounds containing fluorobiphenyl group
DE3510432A1 (de) * 1985-03-22 1986-09-25 Merck Patent Gmbh, 6100 Darmstadt Cyclohexanderivate
DE3510434A1 (de) * 1985-03-22 1986-09-25 Merck Patent Gmbh, 6100 Darmstadt Cyclohexanderivate
JPS61268646A (ja) * 1985-05-24 1986-11-28 Ube Ind Ltd ２−フエニルシクロヘキサノン誘導体
DE8705015U1 (de) * 1987-04-04 1987-11-05 Nsm-Apparatebau Gmbh & Co Kg, 6530 Bingen Münzbetätigtes Spielgerät
US4910350A (en) * 1987-09-29 1990-03-20 Dainippon Ink And Chemicals, Inc. Fluorine-substituted cyclohexylcyclohexene derivative
US4946986A (en) * 1988-02-29 1990-08-07 Dainippon Ink And Chemicals Cyclohexene derivatives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3838172A (en) * 1967-08-22 1974-09-24 Ortho Pharma Corp Aryl substituted-hydroxy substituted cyclohexanecarboxylic acids
GB1325056A (en) * 1969-08-22 1973-08-01 Bristol Myers Co Phenyl-cyclohexane carboxylic acids and derivatives thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4016130C2 (de) * 1990-05-18 2000-06-21 Merck Patent Gmbh Phenylcyclohexane und flüssigkristallines Medium

Also Published As

Publication number Publication date
EP0261160A1 (fr) 1988-03-30
EP0261160B1 (fr) 1991-03-06
DE3703145A1 (de) 1988-08-18
US5068389A (en) 1991-11-26
JPS63502831A (ja) 1988-10-20
DE3768393D1 (de) 1991-04-11

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